Nondyeing sulphurized phenol



Patented Dec. 25, 1934 u I UNITED STATES PATENT oFFicE Frederick B. Downing, Carneys Point, N. J., Richard G. Clarkson, Wilmington, Del., and Chester W. Hannum, Chicago, 111., assignors to E. I. du Pont de Nemoi rs & Company, Wilmin'gton, Del., a'corporation of Delaware No Draiaving. Application November 15, 1932,

s s I Seria l-No. 642,760

8 Claims. (01. 260-20) This invention relates to a process for prountil no more'phenol passed over. The reaction ducing sulphurized derivatives of phenols and mixture was then cooled, broken up and ground more particularly refers to a process of producto a fine powder. In this form it was avery light in? sulphurized phenols which do not discolor gray in color. When dissolved in water with title a rics. aid of a little soda ash it gave a ligh greenis It has heretofore been known that the prodbrown solution. Cloth treated with such a solua ucts produced by treating alkali phenolates with tion exhibited great afiinity for basic dyes and sulphur at elevated temperatures are especially gave much brighter dyeings than when moradvantageous in fixing basic dyes upon cotton. danted with sulphurized phenol prepared in However, this advantage was decreased to a great other Ways.

extent because of the fact that the sulphurized phenols imparted a yellow stain to the cotton 3 upotn P f g In 13 to avold fi A mixture of 1 mole (122 g.) of crude xylenol 1 fi: P i propose 0 use varying and 3 moles (282 g.) of phenol was treated with 2 1 5 1 T Q i a g g 1 mole (40 g.) of powdered sodium hydroxide 1 1 ,z z it i z g a g and was then heated tol80 C. to remove water.

.2? 5 9 2 6 335 8 c u 5 atoms (160 g.) of sulphur were added and the i; ea m m new 1 cul Smce t e preparation continued as in Example 1. After p enol left reactlon betweel? the alkah the completion of the reaction, the mixture was the phenol rapldly corroded plant vacuum distilled to remove excess phenol. The '20 l b j Whlch were product, after cooling and grinding, was areddish gig gzfizi gg gg g g fi g powder, soluble in aqueous alkalies. It possessed ment. Where a higher proportion of alkali to h power of fixmg basic colors m a mgh degree' phenol was used the corrosion was correspondj Example 3 ingly decreased but the product stained cotton A tu f 01' (54 of e 1 d material on which it was impregnated, almost as mlX re 0 2 m e badly as if it were made by the original process. /2 moles 0f phenol (329 8-) w a d-together It is an object of this invention to provide a Wlth 1 mole (40 of Sodmm ydr e and method for producing a nondyeing sulph d 5 atoms (160 g.) of sulphur as described in the derivative of phenol Whlch W111 not stain cotton us xamp es. E cess phenol w o ed or other textile material and which does not rey i taam distillation as giiiletn in Exampl; 1. 'Ihe uire ex ensive e ui ment. Additional ob'ects 6009 pro 110 was groun 0 a p 6 P P W 3,111 appear heremgfign J which was soluble in aqueous alkali and possessed 35 These objects are accomplished by the present the power 0f fixing basic Colors- 36 invention wherein an amount of ulphur mm. It 15 to be understood that other derivatives cient to react with all the phenol present is used, a d o u s o phenol than those ed the excess free phenol being removed by suitable m i he g l p ii g z g fitf means pa mg r m e s o e o 5 ve ion.

40 The invention may be more fully und t d Among these derivatives may be mentioned alkyl, 40 by reference to the following illustrative a a d nitro titut d ph nols.

In carrying out the process of the present inven- Example 2 examples:

tion the derivatives of phenol may be used sepa- Example 1 rately or they may be mixed together in any A mixture of 4 moles of phenol (376 g.) and 1 desired proportion- 45 mole (40 g.) of powdered sodium hydroxide was n general. any of the W611 known alkalies y heated to 180 C., at which temperature water be substituted for sodium hydroxide in practicwas evolved and sodium phenolate formed. To ing the present invention. A few examples of the molten mass was added, little by little, 5 alkalies falling within this class are potassium,

atoms (160 g.) of sulphur and the whole heated barium, lithium, and strontium hydroxides. It 50 at 182 C. with agitation under a reflux conis also to be understood that the amount of a1- denser until the evolution of hydrogen sulphide kali used may be varied within rather wide limits.- had ceased. This took about 15 hours. The re- For instance, merely enough alkali may be added flux condenser was removed and superheated to facilitate sulphurization of the phenol. It is steam was then passed through the molten mass preferable, however, to maintain the molecular 55 proportion of alkali to phenol within the range of about one-fifth to about one-half.

As the atomic proportion of sulphur to phenol (atoms sulphur) 1 (moles phenol) was decreased below 1.5a marked improvement in color took place. When this proportion dropped below 0.9 it was found that the color no longer became lighter, and the yield of sulphurized product had decreased considerably. Consequently, in order to maintain the maximum yield and at the same time produce a product which does not stain cotton or other textile fabrics, the ratio between 0.9 and 1.3 is preferred. However, if a higher yield is desired the upper limit may be increased slightly without imparting a too noticeable stain to the material. This preferred range of 0.9 to 1.3 may be somewhat increased or decreased depending upon the particular phenol or phenolic compounds which are being sulphurized, without-departing from the scope of the present invention.-

The free phenol may be removed at the end of thereaction by any suitable means, such as ordinary distillation, vacuum distillation or steam distillation. I

It is believed that the reason for the excellent results accomplished by the present invention in comparison with results formerly produced is that the presence of a greater amount of sulphur than that specified herein causes the formation of more highly sulphurized derivatives which impart objectionable colors to the impregnated material. By the herein described invention the formation of these more highly sulphurized derivativesis either entirely prevented or greatly decreased,,resulting in the production of a sulphurized derivative which imparts no stain to the textile material.

The process described herein produces sulphurized derivatives of phenol which are very useful as mordants for basic dyes and which in addition do not stain the mordanted material. These products are also useful when treated with sodium bisulphite and formaldehyde as resists for silk and wool, since they do not stain the silk and wool, as was the case when sulphurized derivatives produced by prior processes were used. The process is also highly advantageous since the use of expensive equipment is avoided.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A process for producing sulphurized derivatives of phenols which comprises reacting a mono:- hydric phenol with an amount of sulphur insufficient to react with all the phenol present in the presence of an alkali metal hydroxide, and subsequently removing the unreacted phenol.

2. A process for producing sulphurized derivatives of phenols which comprises heating a monohydric phenol with sulphur, the atomic proportion of sulphur to phenol being not greater than 1.3 1, in the presence of an alkali metal hydroxide, and subsequently removing the unreacted phenol.

3. A process forv producing sulphurized derivatives of phenols which comprises heating a monohydric phenol with sulphur, the atomic proportion of sulphur to phenol being within the range of 0.9 1 to 1.3 1, in the presence of an alkali metal hydroxide, the proportion of alkali to phenol being within the range of 0.2 to 0.5, and removing unreacted phenol.

4. A process for producing sulphurized derivatives of phenols which comprises heating a mixture of a. monohydric phenol and a monohydric phenolate with sulphur, the atomic proportion of sulphur to original phenol prior to the production of phenolate being within the range of 0.9:1 to 1.321, and subsequently removing the unsulphurized phenol.

5. The product produced according to the process of claim 1.

6. The product produced according to the process of claim 2.

7. The product produced according to the process of claim 3.

8. The product produced according to the process of claim 4.

FREDERICK B. DOWNING. RICHARD G. CLARKSON. CHESTER W. HANNUM. 

